Alpha olefin sulfonate detergent compositions

ABSTRACT

HIGH PERFORMANCE DETERGENT COMPOSITIONS CONSIST OF STRAIGHT-CHAIN OLEFIN SULFONATES, AN ALKALI METAL OR AMMONIUM GROUP PENTAVALENT PHOSPHORIC ACID SALT AND AN ALKZANOL-1.

United States Patent 3,565,809 ALPHA OLEFIN SULFONATE DETERGENT COMPOSITIONS Samuel H. Sharman, Kensington, Calif., assignor to Chevron Research Company, San Francisco, Calif., a corporation of Delaware No Drawing. Filed Nov. 27, 1967, Ser. No. 685,948 Int. Cl. C11d 3/07, 3/066 US. Cl. 252137 8 Claims ABSTRACT OF THE DISCLOSURE High performance detergent compositions consist of straight-chain olefin sulfonates, an alkali metal or ammonium group pentavalent phosphoric acid salt and an alkanol-l.

BACKGROUND OF THE INVENTION Field of the invention The present invention is concerned with the field of biodegradable sulfonate detergents and more particularly with readily biodegradable olefin sulfonates having improved detersive characteristics.

Prior art SUMMARY OF THE INVENTION Unexpectedly, it has now been found that ternary mixtures of olefin sulfonates containing 11 to 19 carbon atoms, alkali metal or ammonium group pentavalent phosphoric acid salts and alkanol-1 compounds containing to carbon atoms selected from the normal and Z-methyl isomers possess unusually high detersive characteristics. In particular, the performance of the described ternary mixtures is significantly greater than would be predicted from a knowledge of the performance of the corresponding binary mixtures or of the components individually. The mechanism by which the olefin sulfonates, alkali pentavalent phosphoric acid salts and alkanols cooperate or interact to produce the improved detersive characteristics is unknown. It is known, however, that all three components are necessary to produce the beneficial effects.

The term olefin sulfonates as used in the present invention represents a composition consisting of from 50- 100% unsaturated olefin sulfonates. When the unsaturated olefin sulfonate portion is below approximately 100%, the balance of the composition comprises substantially hydroxy sulfonates. Other compounds may also be present in minor amounts due to impurities in olefin feedstock or as the result of Sulfonation side reactions. The relative proportions of hydroxy and unsaturated sulfonate will vary depending upon the method of preparation. That is, for example, by one method as described in Turbak, A. R, et al., Reaction of Phosphate-Complexed Sulfur Trioxide With Alpha-Olefins, Industrial and Engineering Chemistry, Product Research and Development 2, No. 3, 229 (1963), an olefin sulfonate comprising substantially 100% unsaturated olefin sulfonate may be prepared.

Usually, the amount of hydroxy sulfonate will range from 0 to 50% by weight of the total olefin sulfonates,

and preferably less than 40%. The unsaturated sulfonates may range from to 100% by weight of total olefin sulfonates. Preferably the unsaturated sulfonates comprise more than of the total olefin sulfonates.

Olefin sulfonates of the present invention are prepared by Sulfonation of straight-chain or normal olefins containing 10 to 24 carbon atoms, usually 11 to 19 carbon atoms and preferably containing 15 to 18 carbon atoms. Single carbon cuts of olefins Within this range may also be employed, for example, hexadecene-l. The olefins may be internal or alpha olefins, although alpha olefins are preferred. Sulfonation may be accomplished by any suitable process which produces the proper range of hydroxy and unsaturated sulfonates.

The preferred method of preparation of olefin sulfonates comprises SO -air sulfonation in a falling film reactor, neutralization and saponification or hydrolysis of the neutralized product. The reaction products of the S0 air sulfonation step may be neutralized with an aqueous alkali solution containing any strongly basic compound such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, the corresponding oxides, carbonates and the like. Sufiicient neutralizing solution is added to provide for the subsequent hydrolysis step. Hydrolysis of the neutralized reaction products yields the olefin sulfonates as defined in the present invention.

Generally, the sulfonation conditions cause migration of the double bond in the unsaturated sulfonates and determine the distribution of the double bond locations. Analysis of an alpha olefin C C carbon cut sulfonated with SO -air and suitable for use in the present invention is illustrated in Table I.

TABLE I Sulfonation also produces a variety of hydroxy sulfonate isomers. Since the beta or 2-hydroxy sulfonates are to some degree insoluble in water, processes which minimize their formation are preferred. A suitable process is described in Marquis et al., Alpha Olefin Sulfonates from a- Commercial S0 Reactor, JAOCS, volume 43, No. 11, pp. 607-614 (1966). British Pat. No. 1,030,648 describes another Sulfonation process which may be utilized.

Olefin sulfonates prepared in accordance with the present invention may be modified by mild hydrogenation to produce hydrogenated olefin sulfonates. Hydrogenated olefin sulfonates alone or in mixtures with olefin sulfonates provide excellent active components suitable for the present invention. Hydrogenation of the olefin sulfonates substantially reduces all of the unsaturated sulfonates to alkane sulfonates with little or no effect on the hydroxy sulfonates. The hydrogenation may be conducted with hydrogen at a pressure of 50-800 p.s.i.g., at a temperature of 45-80 C. for 60 minutes over 5% Pd on carbon or barium sulfate as a catalyst.

The primary alkanol component of the detergent composition contains 10 to 15 carbon atoms. The preferred alkanols have the normal or the 2-methyl isomer configuration. Suitable alcohols include decanol-l, undecanol-l, dodecanol-l, tridecanol-l, tetradecanol-l, pentadecanol-l, 2-methyl nonanol, 2-methyl decanol-l, 2-rnethyl undecanol-l, Z-methyl dodecanol-l, 2-methy1 tridecanol-l, and 2-methyl tetradecanol. The preferred alkanols may be added separately or in any combination, for example, 75% dodecanol-l and 25 2-methyl dodecanol-l.

The suitable pentavalent phosphoric acid salts include the tripolyphosphates, pyrophosphates, metaphosphates and orthophosphates. The cation portion of the phosphates may be sodium, potassium, ammonium and the like. For example, suitable phosphates would include, but are not limited to: sodium tripolyphosphate, potassium tripolyphosphate, ammonium tripolyphosphate, tetrasodium pyrophosphate tetrapotassium pyrophosphate, trisodium phosphate, tripotassium phosphate, ammonium phosphate, sodium 'hexametaphosphate, potassium hexametaphosphate, ammonium hexametaphosphate, monosodium orthophosphate, monopotassium orthophosphate, disodium orthophosphate, dipotassium orthophosphate and the like.

The ternary mixtures of the present invention may be prepared in the usual manner known in the art. The order of combining the ingredients is immaterial. The mixtures so prepared may be utilized as effective detergents if desired. Preferably, however, the detergent compositions of the present invention are incorporated with other ingredients into detergent formulations.

The prescribed quantity of surface active ingredient present in a detergent formulation generally consitutes from about to 35% by Weight of the total detergent formulation. The olefin sulfonates of the present invention may likewise be utilized in the same concentrations, although preferably from 15 to 25%. Correspondingly, the amount of olefin sulfonate employed in a detergent formulation will determine the range of the pentavalent phosphoric acid salt and alkanol-l.

An effective amount of alkali pentavalent phosphoric acid salt usually comprises from about A to 3 parts by weight per part of olefin sulfonate. Preferably, the ratio is l to 2 parts by weight per part of olefin sulfonate.

The selected alkanols or mixtures thereof may comprise from about 4 to 40 parts by weight per hundred parts of olefin sulfonate. The most desirable ratio is usually from 8 to 30 parts by weight per hundred parts of olefin sulfonate.

Additional compatible ingredients may be incorporated into the detergent compositions prepared in accordance with the present invention to enhance their detergent properties. Such ingredients may include, but are not limited to, anticorrosion, antiredeposition, chemical bleaching and sequestering agents; optical Whiteners and certain inorganic salts other than phosphate, such as inorganic sulfates, carbonates or borates. The appropriate quantities and compositions of these additives, agents and builders are well described in the art.

An effective means for evaluating the detersive characteristics or detergent compositions is known as the Hand Dishwashing Test which is based on a procedure presented at the ASTM D-12 Subcommittee on Detergents, Mar. 10, 1949, New York, N.Y. The test measures under simulated home washing conditions the number of plates or dishes washed before the foam collapses. This test was utilized to evaluate the improved performance of the disclosed detergent compositions.

Detergent formulations were prepared from the ternary mixtures of the present invention by the addition of water alone or with other ingredients. The formulations were adjusted until the percentage of alcohol and olefin sulfonate equalled 25% by weight of the total detergent formulation.

In the following examples, the concentrations employed in the Hand Dishwashing Test were 0.15% by weight of the total detergent formulation.

Example 1 illustrates a suitable detergent formulation prepared from the ternary mixtures of the present invention.

EXAMPLE 1 A detergent formulation was prepared containing the following percentages of each ingredient, based on the total Weight of the formulation:

Formu- Ternary lation, mixture, percent percent Alpha olefin (Ow-C13) sulionate Sodium tripolyphosphate Dodeeanol-l Sodium silicate Carboxy methylcellulos Sodium sulfate Water TABLE II.-MIXTURE COMPOSITION IN WEIGHT PE RCENT Phos- Sulfo- Dodeephate nate 1 anoll Plates 2 Example 1 Alpha olefin sulfonate 015"018 carbon cut.

2 As measured by Hand Dishwashing Test.

3 Sodium tripolyphosphate.

4 Trisodium phosphate.

5 Tetrasodium pyrophosphate.

Includes inert builders such as sodium silicate, carboxy methyl-cellulose and sodium sulfate.

Tables III and IV represent data obtained from formulations containing all three components. Both tables illustrate the importance of alcohol concentrations on dishwashing ability.

TABLE III.TE RNARY MIXTURE COMPO- SITION IN WEIGHT PERCENT Phos- Sull'o- Dodee phate 1 hate 2 anol-l Plates 3 1 Sodium tripol hosphate. 2 Alpha olefin sulfonate 015-018 carbon cut. 3 As measured by Hand Dishwashing Test.

TABLE IV.-TERNARY MIXTURE COMPO- SITION IN WEIGHT PERCENT Phos- Sullo- Dodeephate 1 nate 1 anol-l Plates 3 Example:

1 Tetrasodium pyrophosphate. 2 Alpha olefin sulfonate 0154315 carbon cut. 3 As measured by Hand Dishwashing Test.

The changes produced in the dishwashing ability of the present compositions by varying the carbon chain length of the alkanol are shown in Table V.

TABLE V n-Alkanol number of carbon atoms Plates Example 1 Ternary mixture composition: phosphate 61%; alkanol 6%; olefin sulfonate 33%.

The dishwashing ability of formulations containing various alcohols is compared with those of the present invention in Table VI Ternary mixture composition: alcohol 6%; phosphate 61%; olefin sulfonate 33%.

Table VII illustrates the dishwashing ability of formulations containing hydrogenated olefin sulfonate alone and in mixtures with olefin sulfonates as the major active components.

TABLE VII.-TERNARY MIXTURE COMPOSITION IN WEIGHT PERCENT l Hydrogenate olefin Olefin Dodecsulfosulio- Plates anol-l nate hate l 62% phosphate.

As will be evident to those skilled in the art, various modifications on this process can be made or followed, in the light of the foregoing disclosure and discussion, without departing from the spirit or scope of the disclosure or from the scope of the following claims.

I claim:

1. A detergent composition having improved detersive characteristics consisting essentially of normal alkali metal or ammonium olefin water-soluble sulfonates containing 11 to 19 carbon atoms,

a pentavalent phosphoric acid alkali metal or ammonium salt in a ratio of about A to 3 parts per part by weight of sulfonate, and

an alkanol-l containing 10 to 15 carbon atoms selected from the class consisting of the normal and 2-methyl isomers in a ratio of about 4 to 40 parts per hundred parts by weight of sulfonate.

2. A detergent composition according to claim 1,

wherein the alkanol-l is dodecanol-l.

3. A detergent composition according to claim 2, Wherein the phosphoric acid salt is selected from the group consisting of sodium tripolyphosphate, tetrasodium pyrophosphate and trisodium phosphate.

4. A detergent composition according to claim 3, wherein the phosphoric acid salt is present in a ratio of about 1 to 2 parts by part of sulfonate.

5. A detergent composition according to claim 4, wherein the alkanol-l is present in a ratio of about 8 to 30 parts per hundred parts by weight of sulfonate.

6. A detergent composition according to claim 5, wherein the alkanol-l is composed of a mixture of the normal and 2-methyl isomers.

7. A detergent composition according to claim 5, wherein the olefin sulfonate is derived from an alpha olefin cut containing 15 to 18 carbon atoms.

8. A detergent composition according to claim 7, wherein the olefin sulfonate comprises a mixture of hydrogenated olefin sulfonates and olefin sulfonates.

References Cited UNITED STATES 'PATENTS 3,332,874 7/1967 Coward et al. 252l37 3,346,629 10/1967 Broussalian 260-613 3,415,753 12/1968 Stein et al 252--121 3,444,087 5/1968 Eccles et al. 252138 FOREIGN PATENTS 588,394 12/1959 Canada 252161 LEON D. ROSDOL, Primary Examiner P. E. WILLIS, Assistant Examiner US. Cl. X.R. 252138 

